In situ 1H nuclear magnetic resonance (NMR) spectroscopy has been used to directly investigate the processes that occur during the early stages (typically the first few monomer addition steps) of an AIBN-initiated reversible addition−fragmentation chain transfer polymerization of styrene in the presence of the RAFT agent cyanoisopropyl dithiobenzoate at 70 and 84 °C. The change in concentration of important dithiobenzoate species as a function of time has been investigated. It was found that the reaction was extremely selective during the period of consumption of the initial RAFT agent (defined as the initialization period), with almost no production of RAFT-capped chains of degree of polymerization greater than unity until all of the cyanoisopropyl dithiobenzoate was converted to its single monomer adduct. The rate-determining step for this process was found to be the addition (propagation) of the cyanoisopropyl radicals to styrene. During the period where the initial RAFT agent was consumed, fragmentation of formed intermediate radicals strongly favored the production of the tertiary cyanoisopropyl radicals, which were the only significant propagating species during that period. This led to a greater rate of propagation during that period, since the propagation rate coefficient for the cyanoisopropyl radical is greater than that of polystyryl radicals. It was found that inhibition effects can occur in the presence of RAFT agents in homogeneous media when the k p for initiator fragments is smaller than for long chain radicals, which is a result of this aspect of the RAFT mechanism.

In situ 1H nuclear magnetic resonance spectroscopy was used to directly investigate the processes that occur during the early stages (the first few monomer addition steps) of azobis(isobutyronitrile)-initiated reversible addition−fragmentation chain transfer (RAFT) polymerizations of styrene in the presence of cumyl dithiobenzoate at 70 and 84 °C. The change in concentration of important dithiobenzoate species and monomer as a function of time was investigated. The predominant type of growing chain under the reaction conditions carries a cumyl end group. The initialization period (the period during which the initial RAFT agent is consumed) in the presence of cumyl dithiobenzoate in homogeneous media was significantly longer than for equivalent reactions using cyanoisopropyl dithiobenzoate as RAFT agent, and the rate of monomer conversion was correspondingly slower. Very strong fragmentation selectivity of the formed intermediate radicals (to form the tertiary propagating radical) was observed during the initialization period. The rate-determining step for the initialization process was the addition (propagation) of the initiator-derived and cumyl radicals to styrene, to form the corresponding single-monomer adducts. The greater length of this period with respect to the same reaction using cyanoisopropyl dithiobenzoate as RAFT agent is suggested to be a result of slower propagation due to a smaller addition rate coefficient of the cumyl radical (which was found to be the dominant propagation process during initialization) to styrene, than for the cyanoisopropyl radical, and to a higher average termination rate for the cumyl radicals than for the cyanoisopropyl radicals. The probable (small) difference in intermediate radical concentration is considered to be a less significant contributor to the length of the period.